JPH03271281A - Production of sulfonyl urea salt,novel sulfonyl urea salt and its use as herbicide - Google Patents

Abstract

PURPOSE: To obtain the subject compound having the remarkably high storage stability and having the properties preferable for the use form, with high purity and high yield by reacting sulfonylurea with an alkali metal hydroxide or a basic organic nitrogen compound in the presence of hydrocarbon as a diluent.

CONSTITUTION: A compound of formula I [R is a halogenoalkyl; R¹ is an alkyl, alkenyl, alkynyl, aralkyl; R² is H, a (halogeno)alkyl, (halogeno) alkoxy, (halogeno) alkylthio, NH₂, mono or dialkylamino; X is N, CH; Y is N, CR³ (CR³ is H, a halogen, CN, alkyl or the like); Z is N, CR⁴ (CR⁴ is R² excluding a halogenoalkylthio and NH₂)], is reacted with an alkali metal hydroxide or a basic organic nitrogen compound at 0-100°C in the presence of hydrocarbon, to form the objective compound of formula II (M⁺ is an alkali metal ion, or the counterion formed by protonation of the basic organic nitrogen compound. The compound of the formula II in which Y is N, is a new material.

COPYRIGHT: (C)1991,JPO

Description

[Detailed description of the invention]

[0001]

[Industrial application field]

The present invention relates to a new process for the preparation of sulfonylurea salts, new sulfonylurea salts, and their use as herbicides. [0002]

[Conventional technology]

Sulfonylurea salts can be obtained by reacting a solution of sulfonylurea in a halogenohydrocarbon solvent with an alkali metal hydroxide or an alkaline earth metal hydroxide and distilling off the potash solvent after optionally filtering it. known (see EP-A 304.382). Since in this process the product generally does not crystallize from solution, it is necessary to distill off the solvent, which requires a large amount of energy and further reduces the chances of obtaining a purification effect. 3-Substituted-1-(2-halogenoalkoxy-benzenesulfonyl)-3-heteroaryl-(thio)ureas are known as herbicides (see EP-A 251.079). However, in aqueous media these compounds undergo relatively rapid hydrolytic degradation. It has not yet been possible to produce salts of these compounds which are more stable and of sufficient quality. [0003]

[Key points of the invention]

This time, general formula (■):

[Chemical formula 5] (I) [In the formula, outer 4 represents a counter ion formed by protonation of an alkali metal ion or a basic organic nitrogen compound,

[4] Mo R represents halogenoalkyl, R1 represents an appropriately substituted group from the series consisting of alkyl, alkenyl, alkynyl or aralkyl, R2 represents hydrogen, halogen, alkyl, halogenoalkyl,
represents alkoxy, halogenoalkoxy, alkylthio, halogenoalkylthio, amino, alkylamino or dialkylamino, X represents nitrogen or -CH group, Y represents nitrogen or 10R group, where R3 is hydrogen,
halogen, cyano, alkyl, formyl, alkyl-carbonyl or alkoxy-carbonyl), Z represents nitrogen or a -CH3 group, where R4 is hydrogen, halogen, alkylhalogenoalkyl, alkoxy,
halogenoalkoxy, alkylthio, alkylamino or dialkylamino)] has been found, and this process is based on the general formula (II).
:[0004]

embedded image (II) A sulfonylurea of [wherein R, R', R2, The method is characterized in that the product is reacted with an alkali metal hydroxide or a basic organic nitrogen compound in a step, and the product obtained in a crystalline form in this step is isolated by a conventional method. Furthermore, it has been found that the sulfonylurea salts of formula (I) produced by the process of the invention are characterized by a strong herbicidal activity. [0005] Formula (I) in which Y represents nitrogen, produced by the method of the present invention
The sulfonylurea salts of are new and likewise form the subject of the present invention as new substances. It must be considered surprising that the sulfonyl salts of formula (I) are obtained by the process according to the invention very simply, in very good yields and in high purity. This is because smooth reaction of polar reactive components in hydrocarbons as non-polar solvents was not expected. Furthermore, comparative experiments have shown that similar reactions in polar solvents lead to the formation of more or less large proportions of decomposition products, and these products are substantially absent in the reaction of the process according to the invention. [0006] In contrast to the corresponding "free" sulfonylureas, the novel sulfonylurea salts exhibit particularly the advantageous properties of extremely stable storage and use forms (compositions and spray solutions). In (I), outer 5 is lithium, sodium or potassium ion, tri(01-C4-alkyl)-ammonium ion, N-(c-c
-cycloalkyl)-N,N-di(01-C4-alkyl)-a6 ammonium ion, or in each case N-(C1-
C4-alkyl)-pyrrolidine, N-(C-C-alkyl)-piperidine, N-(C1-C4-alkyl)-morpholine, N, N'-di(01-C4-
alkyl)-piperazine, N,N-di(01-C4-
alkyl)-benzylamine, 1,5-diazabicyclo-[4,3,01-Raney-5-ene (DBN) 1
．． 8-Diazabicyclo-[5,4,0)-undece-7
-ene (DBU) or 1,4-diazabicyclo-[
Indicates the counter ion formed by protonation of 2,2,2,1-octane [DABC○],

[0007] R represents halogeno-C1-C4-alkyl, R is 01
~C6-alkyl (which can optionally be fluorine, cyano, C1-C
C3-C6-alkenyl and C3-C6-alkynyl, optionally substituted by fluorine or chlorine, or phenyl- 1-C2-alkyl (which may optionally be fluorine, chlorine, nitro, cyano, methyl, methoxy or C1-C2-
phenyl moiety is substituted with alkoxycarbonyl), and R2 is hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, ethylthio, amino, methylamino, ethylamino, Dimethylamino or diethylamino, X represents nitrogen or a -CH group, Y represents nitrogen or a -CH3 group, where R3 is hydrogen, fluorine, chlorine, bromine, methyl, formyl, acetyl, methoxycarbonyl or ethoxycarbonyl and Z represents nitrogen or a -CH4 group, where R4 is hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, propoxy, inpropoxy, difluoromethoxy, methylthio, ethylthio, methyl a method for producing a sulfonylurea salt of amino, ethylamino, dimethylamino or diethylamino);
and when Y represents nitrogen, it relates to a novel sulfonylurea salt. [0008] In particular, the present invention provides formula (I) in which the outer 6 represents a sodium ion or a potassium ion, or trimethyl-triethyl-tripropyl- or tributyl-
Ammonium ion, or N,N-dimethyl-N,N
-diethyl- or N,N-dipropyl-cyclopentylammonium ion, N,N-dimethyl-N,N-
dinityl or N,N-dipropyl-cyclohexylammonium ion, or in each case N-methyl-N-ethyl- or N-propyl-pyrrolidine,
N-methyl-N-nityl or N-propyl-piperidine, N-methyl-N-nityl or N-furopyrumorpholine, N, N'-dimethyl-N, N'
-diethyl- or N,N'-dipropyl-piperazine, N,N-dimethyl-N,N-diethyl- or N,N-dipropyl-benzylamine, 1,5-diazabicyclo["4.3.Of-none5 -en (DB
N) 1,8-diazabicyclo-[5,4,01-
undec-7-nine (DBU) or 1,4-diazabicyclo-[2,2,2,1-octane (DABC○)
indicates the counterion formed by the protonation of

[Outside 6
] O [0009] R represents difluoromethyl or trifluoromethyl, R1 represents methyl, R2 represents hydrogen, chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, ethylthio, methylamino, represents ethylamino or dimethylamino, X represents nitrogen, Y represents nitrogen or a CH group (especially preferably nitrogen), and Z represents a C-R4 group, where R4 is hydrogen, chlorine, methyl, ethyl, The present invention relates to a method for producing a sulfonylurea salt of trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino), and a novel sulfonylurea salt when Y represents nitrogen. . [0010] For example, 3-(4,6-dimethoxy-pyrimidine-2-
yl)-3-methyl-1-(2-difluoromethoxy-
Using (phenylsulfonyl)-urea and trimethylamine as starting materials, the reaction course of the process according to the invention can be summarized by the following equation:

embedded image Formula (II) gives a general definition of the sulfonylureas to be used as starting materials in the process according to the invention for preparing compounds of formula (I). [0011] 2 In formula (II) R, R, R, Preferred or particularly preferred has the meaning already given above. An example of the starting material of formula (II) is shown in Example 1 below.

[Chemical formula 8] (II) [0012]

[Table 1] Table 1 Examples of starting materials for formula (11) RR' R2X Y ZCF
3 CH30CH3N CHC-10CH
3C'r;3 CH3CH3N N
C-QC) 13CF3 CH:i 0CH3
N CHC・-ClCF3 CH
3C2H5N CHC-0CH3C
F, CH, CH, N CHC-・-○C2
H3CF, C1,CH3N
CHC-OCH:tCF3 CH3CH3N
CHC・-C)(3C)'3
(] F(:s CH3N
CM CClCF3 C
)1. CH,N CHC-0CH3CFI
F 2 CH30r", H, N
CHC-Cl[0013]

[Table 2] 9Table 1. : (continued) F<R' R2X Y
ZCHF 2 CH30CH3N
CHCOCH3C11F'zcII
:+C)13
N N
C-・CH3Cor 2 [] 1
3 CT (3N
N C---OCH3C
IIF2 CTJ3 0CI:, N
N C-○CH3CtoIF'z
CH: (C) 3 \
CHC-OCH3CF3 (,
'I(3CH3N N C-CH5C
F, Cfh C2H, N N
C-0CH3CF3 CH3CH3N
N C0CzI]5CF3 CH30
CH3N N C-〇C1]3CF3
CH3QC2H9N N C-0C
2H. CF3 C1130CH3N N
C-NHCH3Cf" 3 CH, 30C
Hz N N
CN11Cz k'sCF”3
CH30CZH,NNC-NHCH
3Cf,, CH3CHl, N
N C-3CH3CF = C1130
CH3N N C--S CH3[00
14] The starting materials of formula (II) are known and/or can be prepared by methods known per se (EP-
(See No. A251,079). The process according to the invention is carried out using alkali metal hydroxides or basic organic nitrogen compounds. Preferred substances are lithium hydroxide, sodium hydroxide and potassium hydroxide,
tri(01-C4-alkyl)-amine, N-(C3
~C6-cycloalkyl)-N,N-G(01~C4
-alkyl)-amine, N-(C1-C4-alkyl)
-pyrrolidine, N-(C-C4-alkyl)-piperidine, N-(01-C4-alkyl)-morpholine, N,
N'-di(01-C4-alkyl)-piperazine,
N,N-di(01-C4-alkyl)-benzylamine 1,5-diazabicyclo-(4,3,0,1-Raney-5-ene (DBN), 1°8-diazapicyclo(5
, 4,01-undec-7-ene (DBU) and 1.
4-diazabicyclo-["2.2.2': l-octane (DABCO). [0015] Particularly preferred materials are sodium hydroxide and potassium hydroxide, trimethyl-trinityl-tripropyl- and tributylamine, N, N-dimethyl-NN-diethyl- and N,N-dipropyl-cyclopentylamine,
N,N-dimethyl-N,N-diethyl- and N,N-
Dipropyl-cyclohexylamine, N-methyl-N-
Ethyl- and N-propyl-pyrrolidine, N-methyl-N-ethyl- and N-propyl-piperidine, N-
Methyl-N-ethyl- and N-propyl-morpholine, N,N-dimethyl-N, N'-diethyl- and N,N'-dipropyl-piperazine, N,N-dimethyl-N, N-diethyl- and N , N-dipropyl-benzylamine, 1,5-diazabicyclo-["4.3.
01-Raney-5-ene (DBN) 1,8-diazabicyclo-[5,4,01-undec-7-ene (DB
U) and 1,4-diazabicyclo-[”2.2.2,
1-o'ytan (DABCO). [0016] The process according to the invention is carried out in the presence of a hydrocarbon as a diluent. Diluents suitable for the process of the invention are aromatic, especially benzene-based hydrocarbons, optionally having 1 to 3 alkyl substituents each having 1 to 3 carbon atoms. Examples of these which may be mentioned are benzene, toluene, o-m- and p-xylene, ethylbenzene, propylbenzene, cumene, 1,2.3-)limethylbenzene 1.2.4-)limethylbenzene and 1,3
．． 5-) Limethylbenzene. Toluene is very particularly suitable as diluent in the process according to the invention. In the process of the invention, the reaction temperature can be varied within a considerable range. Generally, the process is carried out at temperatures between 0 and 100<0>C, preferably between 10 and 50<0>C. Generally, the method according to the invention is carried out under atmospheric pressure. However, it is also possible to carry out the process under elevated or reduced pressure. For carrying out the process according to the invention, 0.9 to 1.5 mol, preferably 1.0 to 1.3 mol, of alkali metal hydroxide or basic organic nitrogen compound are used per mole of sulfonylurea of formula (I). used for [0017] The reactants can be combined in any desired order. In a preferred embodiment of the process according to the invention, the sulfonylurea of formula (I) is first stirred with a hydrocarbon diluent and then the alkali metal hydroxide or basic organic nitrogen compound is added. The reaction mixture is stirred until crystallization of the product is substantially complete. The product is then isolated by suction filtration. The active compounds of formula (I) can be used as defoliants, desiccants, eradicators of broad-leaved plants, in particular as weed killers. Weeds are to be understood in a broad sense as any plant that grows in an undesirable location. Whether the substances according to the invention act as general or selective herbicides depends primarily on the amount used. The active compounds according to the invention can be used, for example, in connection with the following plants [0018] Types: Mustard, Beanumbaina,
The genus Yaegura, the genus Chickweed, the genus Antimys,
Chrysanthemum genus, Chenopodium genus, Nettle genus, Kion genus, Millet genus, Purslane genus, Onamia genus, Compolvulus genus, Sweet potato genus, Polygonum spp., Nettle spp. , genus Prunus genus, genus Crabculina, genus Porphyra, genus Stagbeetle, genus Prunus genus, genus Emetchus, genus Datura, genus Violet, genus Prunus genus, genus Poppy,
Cornflowers, Cornflowers, Trifoliums, and Dandelions. [0019] Double=store■1 oi': Cotton genus, soybean genus, Swiss chard genus, Datura genus, Phaseolus genus, Enthus genus, Solanum genus, Linum genus, Sweet potato genus, Vicia genus Nicotiana genus, Tomato genus, Peanut genus, The genus Piloudomillae, the genus Acanthus, the genus Chicuri, and the genus Capocha. [0020] '-f7 = ol: Millet genus, Verbata genus, Millet genus, Helicoptera genus, Cyperus genus, Strawberry genus, Cyperus genus, Fiscus genus, Pillow millet genus, Helicoptera genus, Psyllium genus, Oat genus, Cyperus genus , Sorghum , Platypus , Aspergillus , Sorghum , Dentsuki , Omodaka , Hawai'i , Firefly , Sphingale , Platypus , Sphunilea , Takanocha , Nukabo , Passagrum , and Apella . [0021] 'Child bamboo'forest's i: Rice genus, Maize genus, Triticum genus, Barley genus, Oat genus, Rye genus, Sorghum genus, Millet genus, Sugarcane genus, Pineapple genus, Acanthus genus, and Allium genus. [0022] However, the use of the active compounds according to the invention is in no way limited only to these types of plants, but extends to other plants as well. Depending on the concentration, these compounds are suitable for the total eradication of weeds; They are suitable, for example, for industrial areas and railway lines, as well as for roads and parks with or without cultivated trees.These compounds are also suitable for perennial cultivation, for example tree plantations, ornamental woodlands, orchards, vineyards, Citrus orchards, nut orchards, banana orchards, coffee orchards, tea orchards, rubber orchards, coconut orchards,
It can be used to eradicate weeds in cocoa orchards, soft fruit orchards and hop fields, lawns, meadows, etc., or to selectively eradicate weeds in annual crops. The compounds of formula (I) according to the invention are suitable for the selective eradication of dicotyledonous weeds in monocot cultivations as a pre- or post-emergence method. The active compounds can be present, for example, in solutions, emulsions, wettable powders, suspensions, powders, dusting powders, pastes, soluble powders, granules, suspensions.
It can be converted into compositions for use such as emulsified concentrates, natural and synthetic substances impregnated with active compounds, and very fine capsules in polymeric substances. These compositions can be prepared, for example, by mixing the active compounds with fillers (i.e. liquid solvents and/or solid carriers) and optionally using surfactants (i.e. emulsifiers and/or dispersants and/or blowing agents). Manufactured by known methods. [0023] When using water as an extender, it is also possible, for example, to use an organic solvent as a co-solvent. Suitable liquid solvents are primarily aromatic substances, such as xylene, toluene or alkylnaphthalenes;
chlorinated aromatic and chlorinated aliphatic hydrocarbons, such as, for example, chlorobenzene, chlorethylene or methylene chloride; aliphatic hydrocarbons, such as, for example, cyclohexane; or paraffins, such as, for example, petroleum fractions; mineral and vegetable oils; Alcohols, such as butanol or glycols, and their ethers and esters; ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water. [0024] Solid carriers include, for example, ammonium salts and ground natural minerals such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as highly dispersed silica, alumina and Silicates are suitable. Solid carriers for adhesives include, for example, crushed and fractionated natural rocks such as calcite, marble, pumice,
Suitable are sepiolite and bitternite, as well as synthetic granules of inorganic and organic materials, as well as granules of organic materials, such as sawdust, coco coir, corncobs and tobacco stalks. Emulsifiers and/or blowing agents include, for example, nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, arylsulfonates, Also suitable are albumin hydrolysis products. Suitable dispersants are, for example, lignin sulphite waste liquor and methylcellulose. [0025] Carboxymethyl cellulose, for example in the form of powder, granules or latex, and natural and synthetic polymers, adhesives such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and natural phospholipids such as cephalin and lecithin, Additionally, synthetic phospholipids can also be used in the compositions. Other additives can be mineral or vegetable oils. Colorants such as inorganic pigments (e.g. iron oxide, titanium oxide and Persian blue) and organic dyes such as alizarin pigments, azo dyes and metal phthalocyanine dyes, as well as e.g. iron, manganese, boron, copper,
Micronutrients such as cobalt, molybdenum and zinc salts can also be used. Generally, the composition is 0. 1-95% by weight, preferably 0
．． Contains 5-90% by weight of active compound. For combating weeds, the active compounds according to the invention can also be used as such or in the form of their compositions as mixtures with known herbicides, finishing compositions or tank mixtures being possible. [0026] Herbicides suitable for the mixture are known herbicides, such as 1-amino-6-ethylthio-3-(2,2-dimethylpropyl)-1,3 for combating weeds in cereals.
,5-) riazine-2,4-(LH,3H)-dione (
amethidione) or N-(2-benzothiazolyl)
-N, N'-dimethylurea (methabenzthiazuron); 4-amino-3- to eradicate weeds in sugar beet
Methyl-6-phenyl-1,2,4-)riazine-5(
4H)-one (methamidron); and 4-amino-6-(1,1-dimethylethyl)-3-methylthio-1,2,4-)riazine- for eradicating weeds in soybean.
5(4H)-one (metribuzin); further 2,4-dichlorophenoxyacetic acid (2,4-D): 4-(2,
4-dichlorophenoxy)-butyric acid (2,4-DB);
2,4-dichlorophenoxypropionic acid (2,4-D
P); N-(methoxy-methyl)-2,6-ethylchloroacetanilide (alachlor); 2-chloro-
4-Ditylamino-6-itupropylamino 1,3.
5-) Riazine (Atalazine); 3-isopropyl-2
, 1,3-benzothiadiazin-4-one 2,2-dioxide (pentacine); methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate (bifenox); 3,5- Dibromo-4-hydroxy-benzonitrile (bromoxynil); 2-chloro-N-([(4-
Methoxy-6-methyl-1,3,5-triazine-2-
yl)-aminoyocarbonyl)-benzenesulfonamide (chlorsulfuron): N,N-dimethyl-N'-
(3-Chlor-4-methylphenyl)-urea (chlortoluron); exo-1-methyl-4-(1-methylethyl)-2-(2-methylphenyl-methoxy)-7-oxabicyclo-(2° 2.1)-Hebutane (synmethyline); 3,6-dichloro-2-pyridinecarboxylic acid (clobiralide); 2-chloro-4-ethylamino-6-(
3-cyanopropylamino)-1,3,5-triazine (cyanazine): 2-[4-(2,4-dichlorophenoxy)-phenoxycoupropionic acid, its methyl ester or its ethyl ester (diclofob): N , N-di-n-propylthiocarbamic acid S-
Ethyl (nibuzyme); 4-amino-6-t-butyl-
3-ethylthio-1,2,4-)riazine-5(4H)
-one (ethiodine): 2-(4-[(6-chloro-2
-benzoxazolyl)-oxycyphenoxy)-propanoic acid, its methyl ester or its ethyl ester (phenoxabrob); 2-[4-(5-)lifluoromethyl-2-pyridyloxy)-phenoxycypropanoic acid or its Butyl ester (fluazifob)
;1-Methyl-3-phenyl-5-(3-)lifluoromethyl-phenyl)-4-pyridone (fluridone): [
:(4-amino-3,5-dichloro-6-fluoro-2
-pyridinyl)-oxycouacetic acid or its 1-methyl-heptyl ester (fluoroxypyr): 2-(4-
C(3-chloro-5-(trifluoromethyl)-2-pyridinyl-oxy]-phenoxy]-propanoic acid or its ethyl ester (haloxyfob); 3-cyclohexyl-6-dimethylamino-1-methyl-1,3 ,5
-) Riazine-2,4-dione (hexazinone): 2-
[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-IH-imidazol-2-yl]
-4(5)-Methylbenzoate (imazamethbenz): 3,5-thiodo-4-hydroxybenzonitrile (ioxinyl): N,N-dimethyl-N'-(4-isopropylfuninyl)-urea (impro Turon):
(2-methyl-4-lylorphenoxy)-acetic acid (MCP
A): (4-chloro-2-methyl-phenoxy)-
Propionic acid (MCPP): N-methyl-2-(1,3
-benzo-thiazol-2-yloxy)-acetanilide (mefenacet); 2-chloro-N-(2,6-
dimethylphenyl)-N-C(IH)-pyrazole-1
-yl-methylcyacetamide (metazachlor); 2-
Ethyl-6-methyl-N-(1-methyl-2-methoxyethyl)-chloroacetanilide-(metolachlor)
:2-([((4-methoxy-6-methyl-1,3,5
-) riazin-2-yl)-amino)-carbonyl]-
(amino]-sulfonyl)-benzoic acid or its methyl ester (metsulfuron);
trifluoromethylphenyl)-(3-ethoxy-4-
Nitrophenyl) ether (oxyfluorfen);
N-(1-ethylpropyl)-3,4-dimethyl-2,
6-sinitroaniline (bendimethalin); 2-chloro-N-isopropylacetanilide (propachlor)
:0-(6-chloro-3-phenyl-pyridazine-4-
) S-octylthiocarbamate (pyridate):
2- [ethyl 4-(6-chloro-quinoxalin-2-yl-oxy)-phenoxycypropionate (quizalofopoethyl); 2-chloro-4,6-bis-(ethylamino)-1,3, 5-) Riazine (simazine): 2
,4-bis-[N-ethylaminocy6-methylthio-
1゜3.5-) riazine (simetrine); 4-ethylamino-2-t-butylamino-6-methylthio-5-)
Riazine (Tilbutrin): 3-4[[(4-methoxy-6-methyl-1,3,5-)riazin-2-yl)-
Methyl amino]-carbonyl]-amino]-sulfonylcutiophene-2-carboxylate (thiameturon): 5
-(2,3,3-trichloroallyl)N,N-diisopropylthiocarbamate (trialate) and 2,6
-Sinitro 4-trifluoromethyl-N,N-dibropynylaniline (triflurawane). Surprisingly, mixtures of species also exhibit synergistic effects. [0027] Mixtures with other known active compounds are also possible, such as, for example, fungicides, insecticides, acaricides, nematocides, avicicides, plant nutrients and soil structure improvers. The active compounds can be used as such or in the form of their compositions or in the use forms prepared therefrom, eg as ready-made solutions, suspensions, emulsions, powders, pastes and granules. These are used in a conventional manner, for example by irrigation, spraying, scattering, etc. The active compounds according to the invention can be applied either before or after emergence of the plants. Furthermore, these can also be mixed into the soil before sowing. The amount of active compound used can vary within considerable limits. This depends primarily on the nature of the desired effect. Generally, the amount used is 1 to 1000g per hectare of soil surface area.
Preferably from 5 to 500 g of active compound. [0028]

【Example】

The following examples illustrate the preparation and use of the active compounds of the invention. Manufacturing example: 2 types of actual production:

[9] 4.4 g (0,010 mol) of 3-(4,6-dimethoxy-S-triazin-2-yl)-3-methyl-1-
(2-)Lifluoromethoxy-phenylsulfonyl)-
The urea was stirred with 15 ml of toluene, then 0.5 ml
g (0.0125 mol) of sodium hydroxide powder were added. The reaction mixture was stirred at 20-25°C for 60 minutes to form a viscous crystalline paste, which was mixed with a total of 30 m
Stirring was maintained by adding 1 part of toluene. After the reaction was completed, the crystalline product was also isolated by suction filtration. 4.0 g (87% of the theoretical value) with a melting point of 224 °C
) of 3-(46-simethoxys-)riazin-2-yl)-3-methyl-1-(2-)lifluoromethoxy-
The sodium salt of (phenylsulfonyl)-urea was obtained. [0029] Implementation temporary lid ceremony:

10. 4.4 g (0,010 mol) of 3-(4,6-simethoxys-)riazin-2-yl)-3-methyl-1-
(2-)Lifluoromethoxy-phenylsulfonyl)-
The urea was stirred with 50 ml of toluene, then 0.8
g of 80% potassium hydroxide powder (0,0114 mol K
OH) was added. The reaction mixture was stirred for 15 hours at 20-25°C and the product obtained as crystals was isolated by suction filtration. 4,1 with a melting point of 193°C (decomposition)
g (86% of theory) of 3-(4,6-simethoxy S
-) riazin-2-yl)-3-methyl-1-(2-)
The potassium salt of (lifluoro-methoxy-phenylsulfonyl)-urea was obtained. Other examples which can be similarly prepared are the compounds of formula (I) shown in Table 2 below.

[Chemical formula 11] (I) [0030]

[Table 3] [00311

[0032] For example, the compound shown in Table 2 as Example 5 can be prepared as follows:

embedded image 8.8g (0.02 mol) (7) 3-(4,6-Simethoxys-)riazin-2-yl)-3-methyl-
1-(2-)Lifluoromethoxy-phenylsulfonyl)-urea was dissolved in 88 ml of toluene by heating to about 40°C and then 2.2 g (0,021
mol) of triethylamine at 35-40°C. The product begins to crystallize after a few minutes. Add this mixture to 2
After stirring for a further approximately 15 hours at 0° C., the crystalline product was isolated by suction filtration. 8.8 g (theoretical value of 82
%) of 3-(4,6-dimethoxy-S-triazine-2
The triethylammonium salt of -yl)-3-methyl-1-(2-)lifluoromethoxy-phenylsulfonyl)-urea was obtained. [0033] Chiri±: ChishidenΔ Post-emergence test solvent: 5 parts by weight dimethylformamide emulsifier: 1 part by weight alkylaryl polyglycol ether additive:
0.1% Lenex-36 (= polyoxyethylene (
6) Tridecyl ether; wetting agent) To prepare suitable formulations of the active compound, 1 part by weight of the active compound is mixed with the above amount of solvent, then the above amounts of emulsifiers and additives are added and the concentrate is Diluted with water to desired concentration. Test plants having a height of 5 to 15 cm were sprayed with the active compound formulation so as to provide the specific amount of active compound desired per unit area. The concentration of the spray solution was chosen to deliver the specific amount of the desired active compound in 1000 liters/ha of water. After 3 weeks, the degree of damage to the plants was evaluated as % damage compared to the expression of the untreated comparison. The numbers indicate: O% = same as untreated comparison without effect) 100% = total eradication In this test, for example Preparations 1, 2, 4, 5, 8
, 9, 10, 11 and 12 have a very strong weed action combined with very good resistance by wheat, barley and corn. [0034]

[Table 5] [0035]

[Table 6] [0036]

[Table 7] [0037]

[0038] Conducted Pre-emergence Test Solvent: 5 parts by weight of acetone emulsifier: 1 part by weight of alkylaryl polyglycol ether To prepare a suitable formulation of the active compound, 1 part by weight of the active compound was added to the above amount. The concentrate was diluted with water to the desired concentration while adding the above amount of emulsifier. Seeds of the test plants were sown in normal soil and irrigated with the active compound formulation after 24 hours. It is convenient to keep the amount of water per unit area constant. The concentration of active compound in the formulation is not critical, only the amount of active compound applied per unit area is decisive. After 3 weeks, the degree of damage to the plants is evaluated as a percentage of damage compared to the expression of the untreated comparison. The numbers indicate: 0% = no effect, same as untreated comparison) 100% = total eradication In this test, for example Preparations 1, 2.4 and 5
The compound has a very strong action against weeds and shows very good resistance by 1Jz wheat, barley and corn. [0039]

[Table 9] [0040]

[Table 10] [0041] Hereinafter, the embodiments of the present invention are as follows: 1゜ Formula 2 general formula:

[Chemical formula 13] (I) [In the formula, outer 7 represents a counter ion formed by protonation of an alkali metal ion or a basic organic nitrogen compound,

[External 7] O R represents halogenoalkyl, R1 represents an appropriately substituted group from the series consisting of alkyl, alkenyl, alkynyl or aralkyl, R2 represents hydrogen, halogen, alkyl, halogenoalkyl,
represents alkoxy, halogenoalkoxy, alkylthio, halogenoalkylthio, amino, alkylamino or dialkylamino, X represents nitrogen or -CH group, Y represents nitrogen or -CR3 group, where R3 is hydrogen, halogen, cyano, Alkyl, formyl, alkyl-
carbonyl or alkoxy-carbonyl) Z represents nitrogen or a -CH3 group, sulfonyl (wherein R4 represents hydrogen, halogen, alkylhalogenoalkyl, alkoxy, halogenoalkoxy, alkylthio, alkylamino or dialkylamino) When producing a urea salt, general formula (II): [0042
] [Formula 14] (II) A sulfonylurea [wherein R, R1, R2, X, Y and Z have the above meanings] in the presence of a hydrocarbon as a diluent at a temperature of 0 to 100 °C 1. A method for producing a sulfonylurea salt, which comprises reacting the product with an alkali metal hydroxide or a basic organic nitrogen compound in this step, and isolating the product obtained in a crystalline form in this step by a conventional method. [0043] 2. In formula (I), outer 8 is lithium, sodium or potassium ion,
tri(C1-C4-alkyl)-ammonium ion, N-(C3-C6-cycloalkyl)-N. N-di(01-C4-alkyl)-ammonium ion or in each case N-(C-C-alkyl)-pyrrolidine, N-(C1-C4-alkyl)-4 piperidine, N-(C1-C4-alkyl) )-morpholine, N,N'-di(01-C4-alkyl)-piperazine, N,N-di(01-C4-alkyl)-benzylamine, 1,5-diazabicyclo-[4,3,0'
l-Raney-5-ene (DBN) 1.8-diazabicyclo-['5.4.0,1-undec-7-ene (D
BU) or 1,4-diazabicyclo-[2,2,2
)- indicates the counterion formed by protonation of octane [DABCO],

[Example 8] MΦ R represents halogeno-C1-C4-alkyl, and R1 is C
-C-alkyl, which is optionally substituted by fluorine, cyano, 6xy or O1-C4-alkylthio; or C-C-alkenyl and C-C-alkynyl, which are optionally substituted by fluorine or 3 6 3 6 is substituted by chlorine), or phenyl-
〇1-C2-alkyl (which is optionally substituted on the phenyl moiety by fluorine, chlorine, nitro, cyano, methyl, methoxy or 01-C2-alkoxycarbonyl), [0044] R2 is hydrogen, fluorine, chlorine, Bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, ethylthio, amino, methylamino, ethylamino, dimethylamino or diethylamino, X represents nitrogen or -CH group, Y represents nitrogen or -CR group, where R3 is hydrogen,
fluorine, chlorine, bromine, methyl, formyl, acetyl, methoxycarbonyl or ethoxycarbonyl). Z represents nitrogen or a -CR group, where R4 is hydrogen,
fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, propoxy, impropoxy, difluoromethoxy, methylthio, ethylthio, methylamino, ethylamino, dimethylamino or diethylamino) The method according to item 1 above for producing the compound of I). [0045] 3. In formula (I), outer 9 represents a sodium ion or a potassium ion, or a trimethyl-triethyl-tripropyl- or tributyl-ammonium ion, or N, N
-dimethyl-N,N-diethyl- or N,N-dipropyl-cyclopentylammonium ion, N,N-
dimethyl-N, N-diethyl- or N,N-dipropyl-cyclohexylammonium ion, or in each case N-methyl-N-ethyl- or N-propyl-pyrrolidine, N-methyl-N-ethyl- or N-propyl -piperidine, N-methyl-N-nityl- or N-propyl-morpholine, N,N'-dimethyl-N. N'-dinityl or N,N'-dipropyl-piperazine, N,N-dimethyl-N,N-dinityl or N,N-dipropyl-benzylamine, 1°5-diazabicyclo[4,3,0]-Raney 5 -en (DBN
) 1.8-Diazabicyclo-[5,4,01-undec-7-ene (DBU) or 1,4-diazabicyclo-(:2.2.21-octane (DABCO) counterion formed by protonation shows,

[9] MΦ R represents difluoromethyl or trifluoromethyl, R1 represents methyl, R2 represents hydrogen, chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, ethylthio, methylamino, represents ethylamino or dimethylamino, X represents nitrogen, Y represents nitrogen or CH group, and Z represents C-R4 group, where R4 is hydrogen, chlorine, methyl, ethyl, trifluoromethyl, methoxy, 2. Process according to item 1 above for producing a compound of formula (I), characterized in that the compound is ethoxy, difluoromethoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino. [0046] 4. General formula (1):

[15] (1) [In the formula, (10) represents an alkali metal ion or a counter ion formed by a basic organic nitrogen compound,

[Example 101 M'' Upon tonification, R represents halogenoalkyl, R1 represents an optionally substituted group from the series consisting of alkyl, alkenyl, alkynyl or aralkyl, R2 represents hydrogen, halogen, alkyl, halogenoalkyl,
represents alkoxy, halogenoalkoxy, alkylthio, halogenoalkylthio, amino, alkylamino or dialkylamino, X represents nitrogen or -CH group, Y represents nitrogen, Z represents nitrogen or -CR group, where R4 is hydrogen,
halogen, alkylhalogenoalkyl, alkoxy, halogenoalkoxy, alkylthio, alkylamino or dialkylamino)]. [0047] 5. In formula (I), outer 11 is lithium, sodium or potassium ion, tri(01-C4-alkyl)-ammonium ion, N-(03-C6-cycloalkyl)-NN-di(01- C4-alkyl)-ammonium ion, or in each case N-(C1-C4-alkyl)-pyrrolidine, N-(C1-C4-alkyl)-piperidine,
N-(C1-C4-alkyl)-morpholine, N, N
'-di(C1-C4-alkyl)-piperazine, N
, N-di(01-C4-alkyl)-benzylamine, 1,5-diazabicyclo-[4,3,0)-Raney 5
-dyne (DBN), 1,8-diazabicyclo-[5,4
, Ol-undec-7-ene (DBU) or 1.4
-diazabicyclo-[2,2,2,1-octane[”D
ABC○] indicates a counter ion formed by protonation, and MO R represents halogeno-C1-C4-alkyl, and R is 01
~C6-alkyl (this can be fluorine, sia, as appropriate), C1~
or C3-C6-alkenyl and C3-C6-alkynyl, optionally substituted by fluorine or chlorine, or phenyl- 1-C2-alkyl (which can optionally be fluorine, chlorine,
Nitro, cyano, methyl, methoxy or 01-C2
- the phenyl moiety is substituted by alkoxycarbonyl), and R2 is hydrogen, fluorine, chlorine, bromine, methyl,
Ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, ethylthio, amino,
represents methylamino, ethylamino, dimethylamino or diethylamino, X represents nitrogen or -CH group, Y represents nitrogen, Z represents nitrogen or -CH3 group, where R4 is hydrogen, fluorine, chlorine, bromine , methyl, ethyl, trifluoromethyl, methoxy, ethoxy, propoxy, impropoxy, difluoromethoxy, methylthio, ethylthio, methylamino, ethylamino, dimethylamino, or diethylamino). Sulfonylurea salt of (I). [0048] 6. In formula (I), the outer 12 represents a sodium ion or a potassium ion, or a trimethyl-trinityl-tripropyl- or tributyl-ammonium ion or N,
N-dimethyl-N,N-diethyl- or N,N-dipropyl-cyclopentylammonium ion, N,N
- dimethyl, N, N-dinityl or N, N-dipropyl-cyclohexylammonium ion, or in each case N-methyl-N-nityl or N-propyl-pyrrolidine, N-methyl-N-ethyl- or N-propyl- piperidine, N-methyl-N-ethyl- or N-propyl-morpholine, N, N'-
Dimethyl-N. N'-diethyl- or N,N'-dipropyl-piperazine, N,N-dimethyl-N,N-diethyl- or N,N-dipropyl-benzylamine, 1°5-diazabicyclo['4.3.0, 1-None-5-ene (D
BN) 1,8-diazabicyclo-[5,4,0'
l-Undec-7-ene (DBU) or 1,4-diazabicyclo-[2,2,2”)-octane (DABC
indicates the counterion formed by protonation of O),

[Formula 12] O R represents difluoromethyl or trifluoromethyl, R1 represents methyl, R is hydrogen, chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, ethylthio, methylamino, represents ethylamino or dimethylamino, X represents nitrogen, Y represents nitrogen, Z represents C-R4 group, where R4 is hydrogen, chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoro 4. The sulfonylurea salt of formula (I) according to item 4 above, which is methoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino. [0049) 7. Formula

[16] [In the formula, outside 13 is shown] sulfonylurea salts of.

[Outside 13] MO is Na” KO or (Cz Hs )3 N
A herbicide comprising HO2 and at least one sulfonylurea salt having the general formula (I) as described in item 4 above. 9. General formula (I) described in item 4 above for eradicating weeds
) use of sulfonylurea salts. 10. A method for producing a herbicide, which comprises mixing the sulfonylurea salt of general formula (I) described in item 4 above with an extender and/or a surfactant. Continued from page 1 [Phase] Int, C1' identification symbol
Internal office reference number C07D 239/47
A 6529-4C2391526529-4
C 251/16 7180-4C
251/22 7180-4C
2531047180-4C 2531067180-4C 2571087180-4C Priority claim [Phase] June 8, 1990 [Phase] West Germany (DE) [Phase] P4018349-1 @ Inventor
Rolf Kirsten Federal Republic of Germany Day-4
019 Monheim, Karl Langhansstrasse n 0 Inventor Joachim Kurth Day of the Federal Republic of Germany - 4019 Langenfeld, Tannenweg
9 0 Inventor Klaus Helm - Day 4000 Düsseldorf 13, Pockt Müller Hackstrasse 55 @ Invention
Person: Day-4019 Monheim 2, Geschwit, Federal Republic of Germany
Stelschoroostrasse 88 @ Inventor Klaus Lürtz Federal Republic of Germany Day-5060 Bergisch Bradbarasen
Ha 2, Augusto Kiel Chebelstrasse 45

Claims (5)

[Claims] [Claim 1] General formula (I): [Chemical formula 1] ▲Mathematical formula, chemical formula, table, etc.▼(I) [In the formula, outside 1 is formed by protonation of an alkali metal ion or a basic organic nitrogen compound. M^■ R represents halogenoalkyl, R^1 represents an appropriately substituted group from the series consisting of alkyl, alkenyl, alkynyl or aralkyl, R^2 represents hydrogen, Represents halogen, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy, alkylthio, halogeno, alkylthio, amino, alkylamino or dialkylamino, X represents nitrogen or -CH group, Y represents nitrogen or -CR^3 group ( where R^3 represents hydrogen, halogen, cyano, alkyl, formyl, alkyl-carbonyl or alkoxy-carbonyl), Z represents nitrogen or -CR^4 group (here R^4 represents hydrogen, halogen, alkyl , halogenoalkyl, alkoxy, halogenoalkoxy, alkylthio, alkylamino or dialkylamino)], general formula (II): [Chemical formula 2] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ( II) A sulfonylurea of [formula R, R^1, R^2, X, Y and Z have the meanings given above] in the presence of a hydrocarbon as a diluent at a temperature of 0 to 100 °C 1. A method for producing a sulfonylurea salt, which comprises reacting with an alkali metal hydroxide or a basic organic nitrogen compound, and isolating the product obtained in a crystalline form in this step by a conventional method. [Claim 2] General formula (I): [Chemical formula 3] ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, the outer 2 is formed by protonation of an alkali metal ion or a basic organic nitrogen compound. [2] M^■ R represents halogenoalkyl, R^1 represents an appropriately substituted group from the series consisting of alkyl, alkenyl, alkynyl or aralkyl, R^2 represents hydrogen, represents halogen, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy, alkylthio, halogenoalkylthio, amino, alkylamino or dialkylamino, X represents nitrogen or -CH group, Y represents nitrogen, Z represents nitrogen or -CR^ 4 groups (where R^4 represents hydrogen, halogen, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy, alkylthio, alkylamino or dialkylamino)]. [Claim 3] Formula: [Chemical formula 4] ▲ Numerical formula, chemical formula, table, etc. are available▼ [In the formula, the outside 3 is shown] A sulfonylurea salt. [Outside 3] M^■ is Na^■, K^■ or (C_2H_5)_
3NH＾■ Claim 4: General formula (I) according to claim 2
A herbicide characterized by containing at least one sulfonylurea salt having the following. 5. A method for producing a herbicide, which comprises mixing the sulfonylurea salt of general formula (I) according to claim 2 with an extender and/or a surfactant.